Process for producing articles of regenerated chitin and the resulting articles



Patented Oct. l5, 1940 UNITED STATES lgx'rialsl"rf-1'!ortica;l y

- l k 2,217,823 PROCESSV Fon 1,ixto'nueluc `ARTICLES orr REGENERATED cHrrrN AND THE RESULT. I INGAMICLESJ f. Clifford J. B. Thor, chicago, 111.,"assignor to The Visking Corporation, C

tion of Virginia l hicago, Ill., a corporalNo Drawing. Original application July 9,21%:)36,` Serial No.-89,768 .V Divided and this application n September 9,1937, Serial'Nc. 163,038 j romains.' (01..:115---5'15l This application is a division of 'myopending application Serial No. 89,768, filed July`9, 1936.

'Ihis invention` relates to' Varticles formedlof regenerated chitin andthe" method of makingv the same. More particularly, this invention 're'- lates to articles of manufacture 'such as filaments, threads, films, tubes, straws, seamless sausage casings, etc.,5form'ed`of regenerated chitinand the method'of producing the same. f i m Chitin is generally consideredtobe -composed of polymerized or condensed mono acetyl hexosamine units. It haslwide'spreadoccurrence in nature as a structuralmaterial chiefly-in arthropod exo-skeletons and in the cell walls of 5 numerous fungi A It is alsoavilable in large quantities from the refuse efcr'ustacean'sheries, which at present i's `of little.` use other 'than as fertilizer and alsoto a limited extent asa high* protein feed stock. Chitin can -be easily removed from materials' containing it 'andpuried' :The common and well-known procedures for obtain# ing chitin from, Aforexampl-e, crustacean refuse consist*- generallyin: converting 'the insolubleV dried. According to this 1 procedure, the residue 'n is a light Lpink or almostwhite aked preparation 1 of relatively pure chitinf `If desired, the-chitin may be bleached. 'I'hough the obtaining and purifying of chitin1is relatively cheap, and even though chitin has some very valuable characteristics, suchasvbeing relatively chemically: inert,

nevertheless chitin hasgup to the present time no extensive commercial use in-the arts; and in- 40 dust/ry. fl `I have found -that by converting'chitiniinto a suitable compound, such as` chitin xanthate, I

ycan regenerate chitin therefrom.'` Thus, `Aby'xextruding the chitin compositions through nozzles ,1 -i or orifices of the desired shapes and sizes into a suitable coagulating and regenerating bath`,,I can produce regeneratedl chitin` articles, such as filaments, threads,y films, ribbons; tubes, -straws,

.l etc.y It is, therefore, an object of this' invention kto provide articles, such as filaments, threads, films,

ribbons, tubes, straws, etc., formedof regenerated chitin.

A further object of this invention is to provide f a method of producing filaments, threads, lms,

ribbons, tubes, straws and the llike of regenerated chitin. l y. i y

specific object'cf this invention is toprovide ars'eamless regenerated chitin sausage casing.

'v 'Other objects: of this invention will become l5 apparent from the following description and appen'dedclaims.v Y 'i` For the 'sake'of convenience, hereafter lthere will be set forth a general procedure for producingarticles of regenerated chitin.` out the process of vproducing these articles, it become'snecessary'to produce several new chitin compounds. It isifto be understood that the` chemical compounds which are produced in carrying out the-preferred embodiment of they;

invention in the making of regenerated chitin.l articlesv aretnot restricted' to the precise use to which they arerputr in this method,but are capable of use for.. many purposes, several of Awhich will also `be hereinafterexplain'ed. zo

To produce, according tomy invention, a regenerated chitin article, chitin obtained Vin any known manner, with or without bleaching asdesired, is treated with a causticA alkali for a suffi-` cient length of time andunder appropriatecon- 25 ditions to produce an" alkali chitin having the desired alkali content, as will behereinafter more fully explained. 'Ihe alkali chitin, preferably after shredding.` and preferably also without aging,l is xanthated. The xanthation may be' 30. c'

viscous, dispersion. of chitinfiianthate, after' -del f f aeration and filtration to remove'foreign subf' stances'jis extrudedfthrough anydesired noz'zle or orifice into a vSuitablel coagulating and 'regenerating bath.v After" regeneration, the regenerated Vchitinarticlej, while in the gelistete, is treated in order'to remove "deleterious'or undesirable compounds producedy during the process. i Y If desired, the articlemay'also be bleached. 'In

the caseof films, threads, `et'cgtl'ie' `products may be treated with a conditioning; agent priorfto' drying, and then thereafter i dried in theusual Inanner. "f f fArticles 'produced Vin the mannerpreviously mentioned are" composed of unchanged chitin. They are non-fibrous, colorless, transparent: and possessv good strength in the 'dryistate ,Chitin products take kup water readily and in so doing its In carrying assume a soft texture and have a slimy feel. Like the original chitin, the regenerated material is insoluble in water, dilute acids, dilute alkalis and all organic solvents.

In order to produce alkali chitin` for example as set forth in my copending; application Serial No. 89,768, filed July 9, 1936, I treat chitin with a caustic solution, preferably by steeping the chitin in a caustic solution. I have found that alkali chitin hydrolyzes so easily that for its formation it is highly preferable and advantageous to employ a steep caustic solution of high concentration and relatively low free water content. By free water content I mean water which is present simply as a free solvent. For example, in a to 50% caustic soda solution, although the Water content is high. it is known that at ordinary temperature conditions a large' proportion of this water is combined with the sodium hydroxide as water of hydration rather than being present simply as a free solvent In the course of my research', I found that chitin treated or steeped with aqueous caustic alkali solutions combinesl with Aincreasing amounts of alkalijdepending 'on the concentration of the steeping caustic solution. The following table shows that the quantity of alkali combining with chitin at roomtemperature (25 C.) increases as the concentration of the steep caust1c increases:

u Equivalents ot Na bound i Percent NaOH in steep caustic per acetyl .u hcxosmuinc unit 28.1 0. l5 30.1 17 31.2 ..23 32.1 .'29 33.0 .41 34.0 .53 34.9 .67 35.9 .71 36.9 75 37.8 .77 38.9 .79 39.8 81 41.0 86 41.9 84 42.8 .88 43.9 .85 45.2 80 46.0 f 85 47.1 9() L 91 .92 .90

While alkali chitin would undoubtedly form in' caustic steeping liquors of concentrations higher than it is believed that this would be impractical and inadvisable, due to excessive amounts of caustic soda'necessarily held by the product in a mechanical Way. n

The extent of combination of chitin with alkali also depends on the temperature conditions. This is particularly the casewhen the lower cor1 centrations of steep liquor are used. .With the lower concentrations, the combination of chitin and alkali is increased if the operation is carried out at lower temperatures. IThuS, for example, the extent of combinationpf alkali with the chitin .is 0.48' and 0.56 equivalents-per acetyl hexe osamine unit when the steeping is carried out at 2 C. to 5 C. and the steep caustic concentrations .are 30.3 and 32.3 respectively. I

In any concentration of steep caustic in which the formation of alkali chitin occurs, the minimum temperature .which may be used is the temperature at which the particular concentration of caustic used in the process would crystallize or solidify. 'I'he maximum temperature which may be employed in the process likewise varies with the concentration of the steep caustic used and is generally limited by the amount of combined a1- kali which may be desired in the alkali .chitin for any specicpurpose. Generally, it is desirable and preferable to work at somewhat below the maximum permissible temperature in any case, since the lower temperatures are not only conducive to increased combination of alkali but also would tend to minimize the possibility of partial deacetylation of the chitin by the alkali. No advantage is to be gained by working above ordinary room or plant temperatures, while reductions in temperature. in so far as practical, would always be an advantage from the chemical standpoint. If, for example, an alkali chitin cony taining0.75 or more equivalents of combined Na per acetyl hexosamine unit is desired, the maximum temperature is somewhat above 25 C. when thecaustic concentration range of the steep' liquor is 40% tov 5,0%, andapproximately 25 C. when the caustic vconcentration range is 3'7 t0 39%, and progressively below 25 C. as the causvtic concentration drops from 37% to 30%.. Thus,

with the caustic steep liquor of appropriate concentration and under theA selected temperature conditions for the required period of time, theex,l cess caustic steep liquoris removed inany convenient manner, such as by pressing. The pressing. may be carried out to remove as much steep liquor as desired. Usually, the pressing -is such as to give an alkalil chitin weighing Aapproximately three times as much as `the chitin originally used. 1

Though the alkali chitin has been previously described as being prepared .with caustic soda steep liquors, itis to;.be understood that other caustic alkali steep liquors mayfbe used. Potassium hydroxide is illustrative .of another caustic alkali which may be employed to produce alkali chitin. When potassium hydroxide is emr ployed, thel conditions-.previously mentioned in connection with the use of `caustic alkali may be used. f' n Alkali chitin may be dispersed in lanaqueous medium.. In order to. disperse alkali chitin in an aqueous medium, the operation should preferably be carried out at a temperature in the neighborhood of 0 C. orlower. One illustrative procedure for dispersing alkali chitin in Water is to mix the alkali chitin `with the desired quantity of crushed ice which, in contact with the caustic soda -in the alkalichitin; provides a freezing mixture.

. Itis obvious thatfthe'final alkali chitin content of the dispersion may be varied within wide lim- Zio its. .Generally,.the alkali-chitin content depends several illustrative specific examples of producing alkali chitin. It is,.ofac0urse, to be understood that the production of. alkali chitin as set forth in the specic examples is the instant invention:

Eramplelf not ylimitative of .300 grams of lchitin flakes, `suchas are pre-` pared'f rom shrimp bran, are steeped in 6 liters of 35% NaOH ,at 0* C. for 2 hours. .Excess caustic solutionr is then removed by pressing. The resulting alkali chitin iskeptcold until. desiredforvfurther use.- It will contain approximately .70 equivalents of combined Na per-acetyl hexosamine unit.

v Exemple n 2 300 grams of chitin flakes lare. ysteeped in 6 alentsY of combined Na peracetyl. hexosarnine unit. A I

.Example 3 V s 300 grams of chitin 'are steeped in`6 liters of 50%v -NaOH lfor 2 'hours at roomtemperat-ure, with'o'ccasional or continuous stirring.' Excesscaustic solution is removed by pressing until the weight 'ofv the 'alkali "chitin-isapproximately 3 times the weight'of the chitin used. It will contain vapproximately .90 equivalents of combined' Na p'er acetyl hexosamine unit.' 'u

, Example 4 VAn unaged press cake of: alkali chitin', asV produced in yExamples'1y2. or'3, is shredded and mixed in a suitable device with 3 to 3.5 kgs. of,

crushedl ice for .1@ hour, whereby an aqueous dispersion of alkali chitin is produced. .It may be kept in .a suitable c'ontainer,preferably. at

near 0 C., until used. Y

As previously indicated, to ,produceaarticlesformed of regeneratedchitin, it is necessaryv to produce chitin xanthate from which the 'chitin is later regenerated. The xanthation of ,chitinv may beV carried, out inseveral ways, for example, as set forth in my copending application Serial No. 89,768, led July 9,1936, and in my application Serial No.Y 163,037, filed September .9, 1937. According to one procedure, a cold dispersion of alkali chitin prepared as hereinbefore described and having the desired chitin and alkali con-` tents, such as, for example, 6% vto 8% of chitin,

is mixed at a temperature of from 10 C. to'

+l5 C. in a suitably jacketed and cooled appar ratus withsuch quantity of carbon bisulphide and for such a time until the desired degree of z xanthation is secured. Generally, the amount of carbon bisulphide employed will be betweenV 1A; f

and 1/2 theweight of the original chitin, and the time, from approximately 2 tof10 hours. There- .-sulting dispersion of chitin xanthateisco'nsider-v ably more stablethan that of the alkali chitin itself, especially at room temperature.

Another procedure for .producing dispersions of chitin xanthate contemplates agitating relatively dry alkali chitin` preferably unaged, .in a

inal chitin fromv 1 to 6 hours. This procedure usually results in a partial xanthation of'the chitin which, however, aids in Vthe dispersion cept after more extended periods of time.l

process. Thereafter, `without removal of any excess carbon bisulphide, the dispersion of the par-l tially xanthated -alkalifchitin'is secured by add# ing'thel desired amountv of water under condi` tions which maintain a temperature betweeny 10 C. and""-"1'5'" C. throughout the mixture.

This can be doneby adding a'll of the water in the formof crushed iceand'y thoroughly -mixing'the same with the partially xanthated chitin. The resulting dispersion may .then ybe further mixed with external cooling, while the xanthation process goes to completion1 or it'fnfiay beallowed to stand in a closed vessel a; cold room at aboutn '0" C. for several hours. After' this stage, a' final thorough mixing is advantageous.

A The ca ustilsoda 'NaOH) content of th'e disfglv persion can be controlled withinI limits'by the concentrationof ythe steepcaustic used in-'the'h production of the alkali chitin, by the addition of weak organicY acids, such as "acetic acid, to neuf tralize part of the caustic so'da, thus reducing-'fits concentration to a lower point, byv theefciency of there'moval ofthe excess steep'caustic, or, if desired,` by 'th'egaddition of caustic soda after the first xanthation treatment. .The addition of y causticfsoda during the' dispersion process is not necessary and usually' undesirable, because the alkali chitin contains an adequate amount. For example, if-the ,chitiniis steeped in 387% NaOH andthe alkali chitin.v pressed to 3, times ther weight 'of the original-'chitin and the quantity` der exactly similar vconditionsusing5.0% steep..

caustic, the NaOHcontent will beapproximately v8% when the chitin content is '7 These figures represent practically the lower limits vof..NaOH concentration,.attainable in, a vfinal. dispersion of 4chitin VLxanthatecontaining 7% of jchitin at the two extremesof: steep caustic concentration,-

betweenr which roomv. .telmperatures steeping A`is successful.

Qbviously,'if rthe .efficiency of the pressing of .the alkali chitin is `less than indi' cated, the alkalicontent of `the final'dispersion vnecessarily. will be greater than these minimum values.l..- 'Ihe chitin xanthate dispersionis .best stored at somewhat .below room temperature. Pro` longed storagey at roomI temperature resultsy in somedeacetylation of thehchitin which may be detrimental to the qualityof vfilms, threads, etc., produced from it. Storage, however, does not result in gelling or precipitation of the chitinyex- The extent of deacetylation 'of the chitin -under such conditionsavaries with the alkali contentof the nal dispersion. 'If the'dispersion of chitin xanthate is`to be used in the 'production' of regeneratedchitinarticles, such as' films', threads, filaments, etc., the dispersion is filtered andfdeaerto extrusion thereof.

xanthate dispersions; I

' Example v5 atedafter the production of :the same'v and prior 300 grams of purified chitin secured in'anyf 'l manner aresteeped in 6 liters of 50% NaOH at closed container with a quantity of carbon bisulphide equal to 'l/; to 1/2 ofthe weight. of the orig.

room temperature (25 C.) for 2 hours. Sufficient excess caustic is removed by'pressing to give a press cake weighing approximately -900 grams.

. The press cakeofalkali chitin is shredded and the unaged shredded alkali chitin is Vmixed with 3 to 3.5 kgs. of crushed ice and 100 cc. of carbon bisulphide. Mixing is continued in a closed mixer at a temperature of not over C. for several hours until the free carbon bisulphide has disappeared.

The resulting viscous dispersion of chitin xanthate, which has a caustic alkali content (NaOH) of 7.5% to 8.4% and a chitin content of 6.6% to 7.4%, is filtered and deaerated.

Example 6 150 grams `of puried chitin obtained in any manner are steeped in 3 liters of 40% NaOH at room temperature C.) or lower for 2 hours. Sufficient excessV caustic is removed by pressing to give a press cake Weighing about 450 grams. The press cake is shredded and then shaken in a closed vessel-with 6D cc. of carbon bisulphide for 4 hours at 25 C., after Which the mixture is transferred to a 1 gallon thermos jug and mixed with 1600 grams of crushed ice. Mixing is continued for 1 hour, then the jug is closed and allowed to stand for 12 to 16 hours. After this period the dispersion is mixed thoroughly, filtered and deaerated. This `dispersion has a caustic alkali content (NaOH) of 6.5% anda chitin content of 7.0%

Example 7 300 grams of purified chitin obtained in any manner are steeped in 6 liters of 50% NaOH at room temperature (25 C.) for 2 hours, after which excess caustic is removed kby pressing to give a press cake weighing about 960 grams. The unaged alkali chitin, preferably after shredding, is shaken in a closed container with 120 cc. of carbon bisulphide for 5 hours at 25 C. The partially xanthated mixture, still containing free carbon bisulphide, is mixed in a power mixer with 3,175 grams of crushed ice for 1/2 hour and then transferred to a container which is closed and kept at near 0 C. for 12 to 16`hours. The dispersion is again mixed inthe mixer for 1 hour, then filtered and deaerated in vacuo. A viscous dispersion of chitin xanthate containing about 7% chitin and 8.5% caustic alkali content (NaOH) is obtained.

When the chitin xanthate composition is to be used in the manufacture of articles of regenerated chitin, it is preferred that the said composition contain 6% to 8% of chitin and 5% to 9% of alkalinity calculated as caustic soda (NaOH), and specifically 7% chitin, and 7%, and preferably 6%, alkalinity calculated as caustic soda (NaOH).

To produce articles of regerenated chitin such as, for example, filaments, threads, films, ribbons, tubes, straws and the like of a chitin xanthate composition, preferably prepared as above mentioned and preferably after filtration and deaeration, is extruded through any desired nozzle or orifice into a suitable coagulating and regenerating bath. If, for example, threads are desired to be produced, the chitin xanthate composition is extruded through well-known spinnerets having orifices ofl a number and size depending on the size of thread to be produced. If films are desired to be produced, then the chitin xanthate composition is extruded through an elongated slot in the bottom of the hopper. When ribbons are desired to be produced, the slot may be of dimensions commensurate with the desired width of the ribbon. Alternatively, a spinneret may be used with a slot of appropriate size. When tubes are desired, the composition is extruded through annular orifices.

The coagulating and regenerating bath may be of the aqueous acid-salt type, preferably containing a mineral acid and a sulphate. Though various mineral acids and salts and mixtures thereof may be used, I prefer to use sulphuric acid and ammonium sulphate. The acid and salt concentrations may vary within wide limits. Aqueous baths containing' 20% to 40% of ammonium sulphate and from 4% to 10% sulphuric acid and specifically of ammonium sulphate and 5% of sulphuric acid have been found to give satisfactory results. Best results have been secured when the aqueous coagulating bath consists of ammonium sulphate and '7.5% of sulphuric acid. It is to be understood that various compounds and substances may also be incorporated in the bath to impart certain described characteristics to the product.

After the chitin has been regenerated, the articles, preferably while in the gel state, are subjected to fluid treatments to remove undesirable substances from the product. For example, the articles are given several water washes and preferably also one including a very dilute solution of an alkali, such as 1/% to 1% of ammonia, to expedite and facilitate the removal of the sulphuric acid.

If desired, the articles while still in the gel state and after washing may be subjected to desulphuring and bleaching operations. desulphuring composition and bleaching composition may be employed. Between the various fluid treatments the product is washed with Water to remove the excess composition or liquor from the product. Finally, the article is dried in any wellknown manner.

If the regenerated chitin article is of the type which requires. conditioning or softening, such as lms, tubes, etc., the softening or conditioning agent isA incorporated into the product in an operation continuous with the process of producing the same. This is usually effected prior to the drying of the article. As a suitable softening agent glycerol may be mentioned. In the preferred embodiment of the invention, the regenerated chitin article is passed through an aqueous bath containing .10% to 20% and specifically 15%l of glycerin prior to drying.

The foregoing procedure, since all of the operations may be carried out in a continuous manner, is admirably suitable and is preferred for the production of regenerated chitin films, tubing, etc.

When filaments or threads or the like are to be produced, this can be accomplished by utilizing the well-known spinning machines of either the bobbin or bucket type. After the threads or iilaments have been collected in or on the selected Any Well-known collecting device, i. e. bobbin or bucket, the packages of yarn may then be subjected to the necessary uid treatments. In the production of yarn, the filaments or threads may be stretched while in the gel state in order to improve the physical properties of the yarn in the same manner as is employed in the production of rayon from regenerated cellulose by either the viscose or cuprammonium cellulose process.

In the production of artificial threads various sizes thereof may be produced, this depending to a great extent on the size of the spinneret orifices. In connection with the production of lms, this too depends to a considerable extent on the size of the slot through which the composition is extruded. Regenerated chitin iilms ranging in thickness from 0.0005f to 0.004" have been produced, though it is apparent that films of greater or lesser thicknesses may also be produced. l

Hereafteris set forth an illustrative procedure for making regenerated chitin articles:

`Erzrample 8 4 orv orifice, whichis preferably submerged, in an aqueous `coagulating 'and regenerating bath c'onsisting of 35%l ammonium sulphate .and 7.57% sulphuric acid. The extruded product is maintained in contact withthe bath until regenerationof A'the chitin" is complete, i. e. until substantially' all brown color is dispersed andthe product is white or grayish rwhite. It is then washed in several changes of water, 1A% of ammonia and Water again, after which it is immersed in 15% aqueous glycerin bath for 15 minutes, squeezed free of surplus glycerin solution, and dried preferably under tension.

Regenerated chitin articles produced as previously mentioned, in addition to possessing the properties also previously mentioned, are 'colorless, transparent and possess good strength in the dry state. Regenerated chitin articles take up water readily and in so doing assume a soft texture and have a slimy feel. Like the original chitin, a regenerated article is insolublein water, dilute acids and all organic solvents.

If it is desired to produce an opaque or low luster product, this can be done by incorporating into the casting or extrudingsolution a pigment or pig ent-like material. For example, titanium oxide, arium sulphate, zinc oxide, antimony oxide, etc., may be incorporated. Likewise, if a colored product is desired, a suitable dyestuff or pigment may be incorporated in the spinning orr casting composition.

If it is desired to produce a moistureproofed regenerated chitin film which can be used as a moistureproof wrapping tissue, the regenerated chitin sheet may be moistureproofed by coating the same with any of the well-known moistureproofing compositions. y 1 y I have found that I can produce flexible, transparent or opaque articles of the type previously described composed of regenerated chitin and regenerated cellulose homogeneously blended together by extruding a composition containing cellulose xanthate or viscose andchitin xanthate and processing said articles as hereinabove described. The properties of such products naturally vary withthe ratio. of chitin to cellulose. When the ratio of chitin to cellulose isras low as 1:2, some of the properties of the corresponding chitin article are still evident.

When the spinning or casting solution contains a high proportion of chitin relative to the cellulose, an acid-salt coagulating bath ofthe type previously described may be used. On the other hand, when the spinning or casting solution contains a chitin content which with respect to the cellulose is low, a coagulating bath of lower acid and salt content may be used.

In addition to the previously mentioned prop,-

erties of flexibility, transparency, etc., regenerated chitin tubing made as previously described possesses severalproperties which make it espelose sausage' casings.

cially suitable forcertain types ofsausage casings. Aj seamless 'regenerated' chitin sausage casing can be produced by extruding chitin xanthate 'compositions through an annular orifice utilizing the processes hereinbefore described and equipment now usedin the production of cellu- For example, thek apparatus and mechanical mode of operation set forth in United States Patents Nos. 1,601,686; 1,612,508,

1,612,509, 1,645,050, 1,654,253, 1,908,892, 1,967,773 and 1,976,438 may be employed. .n Y

The wall thickness of the sausage casing may vary within wide limits, for example from 0.0005" to 0.004. Invthe preferred embodiment of the invention, however, it is preferred that sausage casings have a wall thickness of the vorder of 0.001.". Seamless regenerated chitin sausage casings, when stuffed with fresh meat, such as ground pork sausage meat, are inclined to shrink down kwith the meat when cooked'inlthel ordi'- nary'fmanner, such as frying', broiling, etc.. and do not interfere to such an extent with the taste, quality or textureof the cooked product as is the case with other synthetic sausage casings now on the market. This is a feature which is not found in any of the synthetic sausage casings now on the market.

Since it is obvious that various changes and modifications may be made in the above description without departing from the nature or spirit thereof, this invention is not restricted thereto except-as set forth in the appended claims.

I claim: l

l. Articles of manufacture such as filaments, threads, films, tubes, straws, etc. formed of a homogeneous mixture of chitin and cellulose, said mixture beingregenerated from a mixture of chitin xanthate and cellulose xanthate.

2. A process of preparing regenerated chitin articles which comprises extruding a chitin xanthate composition into an aqueous acid coagulating and regenerating bath through an orifice of a size and shape conforming to the size and shape of the desired article, subjecting the resulting article to fluid treatments, and drying.

3. A process of preparing regenerated chitin articles which` comprises extruding a chitin xanthate composition into an aqueous acid coagulating and regenerating bath through an orifice of a size'and shape conforming to the size and shape of the desired article, subjecting the resulting article to fluid treatments, incorporating a softener in saidy article while it is in the gel` agulating and regenerating-bath containing of ammonium sulphate and 7.5% Voi.- sulphuric acid through an orifice of a size and'shape conforming to the size and` shape of the desired article.

6. A processo! preparing regenerated chitin articles which comprises extruding achitin xanthate composition containing 6% to 8% of chitin and having an alkalinity. calculated as NaOH,

of '5% to 9% into an aqueous acid coagulating and regenerating bath through an orice of a size and shape conforming to lthe size and shape of the desired article. subjecting the resulting article to fluid treatments. and drying. v y

7. A process of preparing regenerated chitin articles which comprises extruding a chitin xanthate composition containing 6% to 8% of chitin and having an alkalinity, calculated as NaOH, of 5% to 9% into an aqueous acid coagulating and regenerating bath through an orice of a size and shape conforming to the size and shape of the desired article, subjecting the resulting article to iiuid treatments, incorporating a softener in said article while it is in the gel state,

and drying.

8. VA process of preparing regenerated chitin articles such as filaments, threads, lms, tubes, straws, etc. which comprises producing alkali chitin, Xanthating said alkali chitin, forming a chitin xanthate dispersion, extruding the chitin xanthate dispersion into a coagulating and re'- generating bath 'through an orifice of a size and shape conforming to the size and shape of the desired article.l

9. A process of preparing regenerated chitin articles such as laments, threads, films, tubes, straws, etc. which comprises -producing alkali chitin, xanthating said alkalivchitin, forming `a. chitin xanthate dispersion, extruding the chitin xanthate dispersion into a coagulating and regenerating bath containing an acid and a salt through an orificeof a size and shape conforming to the size and shape of the desired article.

10. A process of preparing articles of manufacture which comprises extrudinga composition comprising cellulose xanthate andchitin xanthate .into an aqueous acid coagulating and regenerating bath through an orifice of a size and shape conformingto the size and shape of the desired article, subjecting the resulting article 

